US3164483A - Particulate refractory material - Google Patents

Particulate refractory material Download PDF

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US3164483A
US3164483A US311247A US31124763A US3164483A US 3164483 A US3164483 A US 3164483A US 311247 A US311247 A US 311247A US 31124763 A US31124763 A US 31124763A US 3164483 A US3164483 A US 3164483A
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mesh
refractory
silicon carbide
slag
mix
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Donald O Mccreight
Albert L Renkey
Davies Bcn
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Harbison Walker Refractories Co
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Definitions

  • This invention relates to refractories, and more particularly to unfired refractories suitable for use in high temperature operations.
  • the refractory material utilized as the lining for a furnace or the like must be compatible with the slag and/ or molten metal, as the case may be, which may potentially contact the lining.
  • Exemplary of the foregoing is the use of an acid refractory in acid open hearth process and the use of basic refractory in basic open hearth processes.
  • in induction furnaces such as those used in melting aluminum, it is conventional to use a high alumina refractory material to have compatibility.
  • the molten metal has a different reactivity relative to the refractory material of the furnace than does the matte or slag, and further the oxidation level of the furnace atmosphere will to some extent govern the penetrating power of the molten metal itself.
  • furnaces for melting copper and copper alloys see, for example, the book Copper, The Science and Technology of the Metal, Its Alloys and Compounds, by Allison Butts, published in 1954 by the Reinhold Publishing Corporation. See, in particular, chapter 10, beginning page 249, entitled Induction Melting of Copper andCopper Alloys. Induction furnaces are reported to operate with a temperature in the metal bath of about 2100 F.
  • unconsolidated material formed in place, as a ramming mix to be used in fabrication of a monolithic refractor brick, and the like.
  • unconsolidated means not formed to a shape before use. It is a particulate material in the sense that it is not soformed.
  • the instant invention is particularly concerned with unfired refractories, Whether they be performed or not,
  • carbonaceous refractories have certain very distinct disadvantages which have severely limited their use. Solid carbon and graphite materials are not only very expensive but are rapidly consumed, particularly in the presence of oxygen and high temperature. Also, they are good conductors of heat thus undesirably permitting expensive furnace heat to be rapidly lost through furnace walls. When carbon powder or graphite is mixed with other materials, such as oxides or silicates in an effort to keep cost down or to minimize other undesirable effects such as oxidation, much is sacrified andlittle is gained.
  • Graphite-containing plastics used in lining foundryladles for example, have poor strength and poor oxidation resistance unless altered with a glassy flux which severely impairs refractoriness and resistance to wetting.
  • the Greene mixture tended to be less dense than desired; and, since carbonaceous material in the resulting refractory struc ture therein disclosed tended to be relatively fiuffy and light, it was quite rapidly oxidized and/ or eroded by the molten material in service, thereby rapidly eating away the interior structure of the material and lessening the useful operating life of'the'installation.
  • a further object of the invention is to provide an unfired refractory material including very finely divided silicon carbide and a fireclay orhigh alumina castable which resists wetting by a variety of metals, melts and slags.
  • another object is to provide an improved plastic
  • yet'another object is to. provide an improved ramming mix particularly useful in forming a rammed monolithic lining for an induction furnace.
  • a further object of the invention is to provide such refractories which, because of their unique density and strengthcharacter'istics, resist oxidation and have sufficient strength as to resist abrasion and erosion in use.
  • this invention is largely predicated on the discovery that'very'fineiy divided silicon carbidecan be incorporated into various fireclay and high alumina mixes without deleteriously affecting the physical properties thereof and with highly beneficial effects.
  • the Fireclay Oastable Base which is used in each of the mixes consists of the following (parts by weight): Oaleined flint clay (80 to 90% about -3 +05 mesh)60; Calcined flint clay (ball mill fines nominally 100% -65 mesh, to +325)5; Calcium aluminate cement (all 100 mesh and about 60 to 75% being 325 mesh)l8; Ball clay or equivalent plasticizcr (all -325 mesh, average particle. diameter is 2 to 5 microns)2.
  • the mixes were cast to 9 x 4 /2 x 2 /2 inch brick and a pocket 1 inch deep and 3 inches in length and width was cut in the 9 x4% inch face. Molten metal or slag was deposited in the cup and held ata predetermined temperature for 5 hours. The brick was then cooled and sawed through the center of the pocket parallel to the 4 2 x 2 /2 inch faces to observe penetration.
  • the B-2 brick (85% of Fireclay CtastableBase) showed about A; inch deep penetration on the surface of the cup and the sides where the boiling nickel matte ran down. Very little corrosion was in the cup; no additional penetration. On the freely exposed sides, the graphite burned out about inch deep. Appearance was fair; most of the metallic charge was retained. The boiling of the slag is probably an indication of gas evolution from the refractory as a result of rapid oxidation of the graphite.
  • the B3 brick (:also 85% of the Fireclay Castable Base) with 15% ball milled pitch was generally similar There was more corrosion, the pitch burned out 1 inchf deep, and
  • Appear- Silicon carbide exhibits high oxidation resistance as compared to amorphous carbon or graphite, and exhibits :a high retardation of molten metal penetration.
  • FIG. l is an enlarged reproduction of cut sections through comparative laboratory test cups','exhibiting'relative resistance to wetting and penetration by molten metal;
  • the material of this invention is nonwettable as is indicated by formation of such a convex meniscus.
  • FIG. 2 is indicative of non-wetting in that a convex meniscus has slag, which have been traditionally difiicult, but also such notorious bad. actors of rather. simple composition such as V 0 and borax.
  • Table HI shows composition. details for Mix B-4 of Table I and Mixes E and F of Table II.
  • the silicon carbide fines used in our invention are preferably about 325 mesh or finer and it is one of the distinctive and surprising features of our invention that such fine material, with high surface area and hence high protective value, can be employed without excessive oxidation loss in the absence of additions of glasses or fluxes to shield from oxidation. It is another surprising feature that the resulting structures are highly resistant to electric current and heat flow despite the silicon carbide inclusion.
  • Such fines are conveniently and inexpensively obtained as reject sizes in the preparation of cutting and polishing tools or as dust collector fines from plants preparing silicon carbide sizes for resale. incorporated within our mixes is the minimum amount which will exhibit the non-wetting melt-resistant eifects desired, the remainder is the aggregate.
  • the upper limit of silicon carbide fines usable is not controlled by loss of the melt resistant effects but rather by considerations such as cost, thermal conductivity, and overall size grading suitable to yield the necessary dense, tight structure essential for the operation of the invention.
  • 5 0% by weight of 325 mesh silicon carbon fines can not be incorporated into a castable mix without undesirably affecting density.
  • Even coarser sizes of silicon carbide are effective in repelling slags and melts, although not nearly as effective as the finer sizes on a weight basis.
  • the refractory composition of this I invention is size graded so that the coarser, +65 mesh portion is the aggregate and the. fines are silicon carbide. Details of the silicon carbide sizing is set forth above.
  • the aggregate is obtained by grinding or otherwise comminuting lump material until it substantially all just passes a 3 or 6 mesh screen. This material is referred to as -3 or 6 mesh material in the art to which this invention relates.
  • the particle distribution curve which is descriptive of percentages on subsequent smaller sieves or screens is, of course, variable, depending on the lump material being considered. As a general rule, though, when to of selected aggregate of this invention has been reduced to pass a 3 or 6 mesh screen, from 50 to 90% is retained on a 65 mesh screen.
  • the sizing of the alumina, aluminum ores, calcined fire clay, quartzite or gannister, and mixtures thereof can therefore be described as follows: 80 to 90% being --3 to 6-mesh with 50 to 90% thereof resting on a 65 mesh screen. The remaining portions of the aggregate are coarser than 3 or 6 mesh and finer than 65 mesh.
  • a particulate, unformed refractory material consisting essentially of, by weight, about 70 to of at least one ingredient material selected from the group consisting of alumina, aluminum ores, and fire clay, said ingredient material being 80 to 90% 3 mesh with 50 to 90% thereof being +65 mesh, and about 5 to 30% of silicon carbide, said silicon carbide being to --325 mesh, said refractory material being free of ingredients which will vitrify at temperatures of about 2100 F.
  • An unfired refractory shape consisting essentially of, by weight, about 70 to 95% of at least one ingredient ma terial selected from the group consisting of alumina, aluminum ores, and calcined fire clay, said ingredient material being 80 to 90% '3 mesh with 50 to 90% thereof being +65 mesh, and about 5 to 30% of silicon carbide, said silicon carbide being 100 to +325 mesh, but at least about 5% being 325 mesh, and said shape being free of ingredients which will vitrify at temperatures of about 2100 F. and resistant to wetting by molten copper and its alloys at this temperature.
  • a particulate, unformed refractory mixture consisting essentially of, by weight, about 85% of fire clay and about 15% of 325 mesh silicon carbide said fire clay being 80 to 90% 3 mesh with 50 to 90% thereof being +28 to +65 mesh, the mixture being free of ingredients which'will vitrify at temperatures of about 2100 F.
  • a high alumina ramming mix consisting essentially of, by weight, about 80% of at least one material selected from the group consisting of alumina and aluminum ores, said material being 80 to 90% 3 mesh with 50 to 90% thereof being +28 to +65 mesh, and about 10% of --325 mesh silicon carbide, said mix being free of ingredients which will vitrify at temperatures of about 2100 F.
  • refractory material of claim 7 in which a major portion of the material slected from the group consisting of alumina, aluminum ores, and fire clay, is about 3 mesh, and the quartzite is about 6 mesh.
  • a particulate, unformed refractory material consisting essentially of, by weight, about 40 to 95% of at least one ingredient material selected from the group consisting of alumina, aluminum ores, and fire clay, said ingredient material being 80 to 90% -3 mesh with 50 to 90% thereof being +65 mesh, and about 5 to 30% of silicon carbide, said silicon carbide being 100 to 325 mesh, and up to about 15 of said fireclay being 325 mesh ball clay as a plasticizer, said material being free of ingredients which will vitrify at temperatures of about 21.00 F.
  • An unfired refractory shape consisting essentially of, by weight, about 70 to 95 of at least one ingredient material selected from the group consisting of alumina, aluminum ores, and calcined fire clay, said ingredient material being 80 to 90% '-3 mesh with 50 to 90% thereof being +65 mesh, and about 5 to 30% of silicon carbide, said silicon carbide being 100 to -325 mesh, but at least about 5% being 325 mesh, and up to about 15 of said fire clay including --325 mesh ball clay as a plasticizer, said shape being free of ingredients which will vitrify at about 2100 F.
  • a particulate, unformed refractory mixture consisting essentially of, by weight, about 85 of fire clay of which up to about 15%, by weight, based on the total weight of the mixture, is -325 mesh ball clay, and about 15 of 325 mesh silicon carbide said fire clay being 80 to 90% 3 mesh with 50 to 90% thereof being +28 to +65 mesh, the mixture being free of ingredients which will vitrify at a temperature of about 2100 F.
  • a high alumina ramming mix consisting essentially of, by Weight, about 80% of at least one material selected from the group consisting of alumina and aluminum ores, said material being 80 to 90% 3 mesh with 50 to 90% thereof being +28 to +65 mesh, and about 10% of 325 mesh silicon carbide, said mix being free of ingredients which will vitrify at a temperature of about 2100 F.
  • An unformed, particulate refractory free of material which will vitrify at temperatures of about 2100 F., and which, when formed, is resistant to wetting by molten copper and its alloys at 2100 F., consisting essentially of 30 to 95% of at least one material selected from the group consisting of alumina, aluminum ores, and fire clay, said material being to -6 mesh with 50- to 90% thereof being +65 mesh, about 5 to 30% of mesh silicon carbide, the remainder of the material being up to about 25% quartzite and up to about 15%, by Weight, ball clay.

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Description

1965 D. o. MCCREIGHT ETAL 3,164,433
PARTICULATE REFRACTORY MATERIAL Filed Sept. 24, 1963 Fug 3 Inventor s m we ,m C I c w MLD 0mm. mm fl MA v 0 B D United States Patent 3,164,483 PARTICULATE REFRACTGRY MATERIAL Donald 0. McCreight, Bethel Park, and Albert L. Renkey and Ben Davies, Pittsburgh, Pa, assignors to Harbison- Walker Refractories Company, Pittsburgh, Pin, a corporation of Pennsylvania Filed Sept. 24, 1963, Ser. No. 311,247 13 Claims. (Cl. 106-44) This application is a continuation-impart of copending application, Serial Number 177,649, filed March 5, 1962, now abandoned in prior of the present application.
This invention relates to refractories, and more particularly to unfired refractories suitable for use in high temperature operations. It is well known and understood in this art that the refractory material utilized as the lining for a furnace or the like must be compatible with the slag and/ or molten metal, as the case may be, which may potentially contact the lining. Exemplary of the foregoing is the use of an acid refractory in acid open hearth process and the use of basic refractory in basic open hearth processes. Similarly, in induction furnaces, such as those used in melting aluminum, it is conventional to use a high alumina refractory material to have compatibility.
Experience in the metallurgical industry has shown that it is not always possible to provide a refractory lining which is highly resistant to both the slag and the molten metal present. In some instances, the chemistry of the slag is such that it is extremely corrosive in contact with a refractory; whereas, the same refractory might be quite satisfactory with the molten metal being treated. The foregoing has been an important consideration in the development of refractories for the linings of the converter in the basic oxygen converter steel process. In this process, the early slag is relatively high in silica; whereas, subsequently formed slag is relatively high in iron oxide with lesser percentage quantities of silica.
In copper producing furnaces, the molten metal has a different reactivity relative to the refractory material of the furnace than does the matte or slag, and further the oxidation level of the furnace atmosphere will to some extent govern the penetrating power of the molten metal itself. For a discussion of furnaces for melting copper and copper alloys and by way of background, see, for example, the book Copper, The Science and Technology of the Metal, Its Alloys and Compounds, by Allison Butts, published in 1954 by the Reinhold Publishing Corporation. See, in particular, chapter 10, beginning page 249, entitled Induction Melting of Copper andCopper Alloys. Induction furnaces are reported to operate with a temperature in the metal bath of about 2100 F.
Depending onwhich metallurgical process the refractory is to be used with, it may be fired or unfired, it may be an unconsolidated material formed in place, as a ramming mix to be used in fabrication of a monolithic refractor brick, and the like. In the art to which this invention relates unconsolidated means not formed to a shape before use. It is a particulate material in the sense that it is not soformed.
The instant invention is particularly concerned with unfired refractories, Whether they be performed or not,
thermal conductivity than their fired counterparts. .-It
.sintering and/or ceramic union between the particulate material used to make it.
It has been recognized by those versed in the art that the most effective refractory lining material would be that which would resist wetting by the molten metal and/ or slag with which it would be in contact in service. Experience has also demonstrated that the inclusion of a reducing agent in the form of amorphous carbon and graphite to refractory monolithic materials (for example, refractory plastics, castables, ramming mixes, and the like) imparts definite resistance to the penetration and wetting by various molten metals and slags. Carbon blocks are another example of prior use of carbonaceous materials.
Generally, carbonaceous refractories have certain very distinct disadvantages which have severely limited their use. Solid carbon and graphite materials are not only very expensive but are rapidly consumed, particularly in the presence of oxygen and high temperature. Also, they are good conductors of heat thus undesirably permitting expensive furnace heat to be rapidly lost through furnace walls. When carbon powder or graphite is mixed with other materials, such as oxides or silicates in an effort to keep cost down or to minimize other undesirable effects such as oxidation, much is sacrified andlittle is gained. Graphite-containing plastics used in lining foundryladles, for example, have poor strength and poor oxidation resistance unless altered with a glassy flux which severely impairs refractoriness and resistance to wetting. And, of 7 course, since graphite and amorphous carbon refractories have high electrical conductivity, their use has been severely restricted in electrically-heated furnaces wherein The patent to Greene, United States Patent Number 1,455,748, disclosed the addition of carbon, or broadly, a carbonaceous material, to MgO or SiO and clay, and 'to use the resulting mixture as an induction furnace lining. However, while satisfactory to some extent, the Greene mixture tended to be less dense than desired; and, since carbonaceous material in the resulting refractory struc ture therein disclosed tended to be relatively fiuffy and light, it was quite rapidly oxidized and/ or eroded by the molten material in service, thereby rapidly eating away the interior structure of the material and lessening the useful operating life of'the'installation.
The patent to Fisher, United States Patent No.
2,141,600, suggests a procedure whereby some of the problems encountered with the Greene mix could be counfractory to which is added an amorphous carbonaceous material, graphite, or possibly an allotropi'c form of carbon such as silicon carbide, a binding agent, and preferably an additional flux material. The sum purport of Fisher appears to be the'provision of a coating overth e' carbonaceous inclusion to thereby slow its loss by oxidation With molten metal or slag. The bonding or bind refractory.
I the mixes tested.
ing an inherent, continuous network of poor resistance through the body, thereby tending to reduce its range of application and its useful life. Fisher also discussed the difiicultiesencountered in providing a suitable refractory for melting copper metal, and suggested that his refractory mix, including a carbonaceous reducing agent, was satisfactory in contact with molten copper since the copper oxide was reduced on contact. In laboratorytests and in actual service installations using refractory compositions including graphite, the graphite was burned out after relatively short periods of operation. In such an instance, the graphite is burned away from the hot face and the refractory then undergoes penetration and corrosion, sometimes completely through the refractory, causing serious and costly shutdown of equipment.
Further, graphite-containing mixes have been found to be typically weak and of low density, making them susceptible to shrinkage cracking in service and erosion by the wash of the copper metal. I r
Accordingly, it is an object of this invention to provide new and improved unfired refractories; which are particularly useful'in fabrication of monolithic structures; which have low permeability, apparent porosity, and resistance to electrical flow and heat flow.
a A further object of the invention is to provide an unfired refractory material including very finely divided silicon carbide and a fireclay orhigh alumina castable which resists wetting by a variety of metals, melts and slags.
Still ,another object is to provide an improved plastic And yet'another object is to. provide an improved ramming mix particularly useful in forming a rammed monolithic lining for an induction furnace. It is another object of the invention to provide refractories for use at high temperature in structures which exhibit exceptional resistance to penetration and corrosion by liquid slags :and metals. A further object of the invention is to provide such refractories which, because of their unique density and strengthcharacter'istics, resist oxidation and have sufficient strength as to resist abrasion and erosion in use.
Briefly, "in one embodiment, this invention is largely predicated on the discovery that'very'fineiy divided silicon carbidecan be incorporated into various fireclay and high alumina mixes without deleteriously affecting the physical properties thereof and with highly beneficial effects.
' about /2 inch deep peripherally of theslag pocket.
.to cup B-2, above, but definitely inferior.
Fireclay Castablc Basc, Percent..-" Fine Graphite, Percent Milled Pitch, Percent Silicon Carbide Fines (-325 mesh) Percent Water Added, Percent Workability 11. 5 1s. 0 15. o All four mixes cast wel; except for B-3 the mixes showed very good overnight set; the set of B-3 was only moderate. Bulk Density, p.c.f., after drying at 230 F. (Av. 5) 131 117 104 131 Modulus of Rupture, p.s.i., after dry- 7 ing at 230 F. (Av. 2) 920 340 470 1,100
I The Fireclay Oastable Base which is used in each of the mixes consists of the following (parts by weight): Oaleined flint clay (80 to 90% about -3 +05 mesh)60; Calcined flint clay (ball mill fines nominally 100% -65 mesh, to +325)5; Calcium aluminate cement (all 100 mesh and about 60 to 75% being 325 mesh)l8; Ball clay or equivalent plasticizcr (all -325 mesh, average particle. diameter is 2 to 5 microns)2.
The mixes were cast to 9 x 4 /2 x 2 /2 inch brick and a pocket 1 inch deep and 3 inches in length and width was cut in the 9 x4% inch face. Molten metal or slag was deposited in the cup and held ata predetermined temperature for 5 hours. The brick was then cooled and sawed through the center of the pocket parallel to the 4 2 x 2 /2 inch faces to observe penetration.
In these tests, nickel matte slag was added and the brick and slag statically tested at 260031 for 5 hours. The B-1 brick (entirely of Fireclay Castable Base) corroded None of slag was retained in the pocket and most of it penetrated almost to the exterior. periphery of the brick. Generally, the appearance was very poor.
The B-2 brick (85% of Fireclay CtastableBase) showed about A; inch deep penetration on the surface of the cup and the sides where the boiling nickel matte ran down. Very little corrosion was in the cup; no additional penetration. On the freely exposed sides, the graphite burned out about inch deep. Appearance was fair; most of the metallic charge was retained. The boiling of the slag is probably an indication of gas evolution from the refractory as a result of rapid oxidation of the graphite.
The B3 brick (:also 85% of the Fireclay Castable Base) with 15% ball milled pitch was generally similar There was more corrosion, the pitch burned out 1 inchf deep, and
' much less of the metallic charge was retained. Appear- Silicon carbide, according to the concepts of this invention, exhibits high oxidation resistance as compared to amorphous carbon or graphite, and exhibits :a high retardation of molten metal penetration.
Other objectsgandfurther features and advantages of unfired refractories according to the concepts of this invention, will become readily apparent to those skilled in the refractory art from a study of the following detailed description with reference-to the appended exemplary drawings. -Inthesedrawings: i
'FIG. l is an enlarged reproduction of cut sections through comparative laboratory test cups','exhibiting'relative resistance to wetting and penetration by molten metal;
I cups ofFIG. 1.
fragmentary detail of the other ance was poor. r v a I The B-4 brick (this too was 85% of the Fireclay Castable Base) with 15% silicon carbide fines showed a little boiling and corrosionon the surface ofthe cup, but none in the cup. There was no penetration; essentially all of the metallic charge was retained; and it had excellent ap pearance.
While additions of graphiteor milled pitch seriously reduced the density and strength of the castable, the addition of our'invention (B 4) resulted in unchanged density and asubstantial improvement in strength. In furnace service, the "lack of density and strength in the graphite and pitch-containing mixes would compound theirdestrucresist a complex CaOSiO P O -K O melt in a newly To investigate the resistance of refractory compositions having-a quantity of very finely divided silicon carbide added thereto, to metal penetration and wetting, and to compare the silicon carbide fines in this respect to other further the composition of developed commercial process. Conventional slag-resistant brick types (A and B) were included as well as two types of graphite-containingmonoliths and two'ex'arnples of monoliths of oupinvention. Mixes C and F are a direct comparison between. fireclay plastics containing graphite Verstisfthdse'of our invention containing silicon Mix D was introduced for further comparison. Mix D contains graphite but no added glass to prevent. oxidation of the carbon. Mix D resisted. the slag much better than Mix C but not nearly' as Well as Mix F. It was also noted that the melt boiled. up in the Mix D cup indicating gas formation due to oxidation of the carbon and, if the test had been of longer duration, Mix D wouldundoubtedly havebeen penetrated by the melt.
While the presence of glass in Mix C was greatly responsible for the rapid slag erosion, comparison of the density and strength figures for Mixes C and F also reveals. an important aspect of the tests. Fireclay and highalumina mixes, containing fine graphite or amorphous carbon, simply cannot be formed to suflicient density and strenth as to prevent oxygen infiltration and erosion by furnace wash. Mixes F and D can be compared in strength but not in density since Mix D used a much denser base grain.
(i been formed. The material of this invention is nonwettable as is indicated by formation of such a convex meniscus.
In actual field tests, the use. of Ramming Mix E of Table II has resulted in a number of cases of more than 100% increased campaign life in low frequency induction furnaces such as discussed by Fisher; while the replacement of Mix C with Mix F in gray iron foundry ladles resulted in 40% better life. These dramatic improvements are the results of a combination of improved nonwetting characteristics and improved physical properties.
The unusual advantages of our invention have notbeen confined, however, to any small group or type of furnace melts but rather have been found to apply to an unexpectedly large range of compositions. Destructive melts controlled by the refractories of our invention not only include complex mixtures such as nickel matte and foundry Table II LABORATORY TESTS WITH COMPLEX CaOSiOzP K2O MELT Cup Slag Test at 2,700 F.
Bulk v Modulus Refractory Density of Rupture Linear (p.c.t.) (p.s.i.) Change Appearance of Test Specimen In Test After Testing Specimen,
Percent A Dense 85% Alumina Brick 179 2,600 0.5 Marked reaction and undercutting at slag line with penetration more than 1 beyond original cup bottom. B Dense Magncsite Brick 183. +0.2 No undercutting at slag line or evidence of reaction with refractory. Slag retention nil, however, all but a surface skin soaking into. specimen.
0 Conventional Fireclay Plastic 129 390 +0.9 Severe undercutting at slag Containing Graphite and line permitted slag toescape Glass to Retard Oxidation. through side ofpocket.
D Conventional 60% A120; Plas- 133 300 +0. 7 v Refractory seemed resistant to tie Containing Graphite and penetration and reaction, No Flux Addition. although slag had boiled up to vesicular mass. Marked undercutting at slag line but no breakout.
E B High Alumina Hamming Mix 175 2, 600- +0. 4 Slight erosion in bottom of cup of Our Invention, Containbut no penetration and ing 10% SiC fines (subessentially all slag retained :stantially all -325 mesh) in cup.. No undercutting at and No Flux. slag hne.
F 2 Fireclay Plastic of Our In- 136 500 +0.9 No. apparent penetration or vention Containing SiC. erosion, of refractory. No Fines (substantially all undercutting at slag l ne. 325 mesh), No Added Essentially allslag, retained Flux. in cup. p
1 Commonly used in slagging applications.
2 See Table III, infra, for the specific composition of Mixes E and F.
-as at 14, penetrated to substantially the bottom of the specimen. In the detail of FIG. 3, the apparent wetting by the slag of the specimen, is indicated by the formation of a concave meniscus.
In contradistinction, specimen 17 retained the slag 18 with no penetration of the walls of slot 19. FIG. 2 is indicative of non-wetting in that a convex meniscus has slag, which have been traditionally difiicult, but also such notorious bad. actors of rather. simple composition such as V 0 and borax.
The fact that. there. is-no chemical common denominator among these various-melt examples strongly supports the highly improved: physical characteristics of refractories according toour invention. Our tests established that fine amorphous carbon orgraphite cannot be successfully substituted for the silicon car-bidefines of our invention.
The tests also established that the silicon carbide fines can be physically incorporated into refractory mixes which have otherwise suitable characteristics ofhigh density, high strength, and resistance to penetration without detriment to such mixes.
Table HI shows composition. details for Mix B-4 of Table I and Mixes E and F of Table II.
Mix B4, Percent Mix E, Percent Mix F, Percent Calcined flint clay (80 to 90% about 3 +65 mesh) Calcined bauxite (Soto 90% about 3 +65 mesh) Quartzite (80 to 90% about 6 +65 mesh) i Calcined flint clay (ball 'mill fines I nominally 100% 65 mesh, 40 to 60% +325). Calcined bauxite (ball mill fines nominally 100% 65 mesh, 40 to 60% +325) Calcium aluminate cement (all -100 mesh and about 60 to 75% being 325 mesh) Ball clay or equivalent plasticizer (all -325 mesh, average particle diameter is 2 to 5 microns) 2 Silicon carbide fines (-325 mesh, average particle diameter is about 1 to 10 microns) Total 100 100 100 The examples above illustrate one each of refractory monolith types falling within the scope of our invention, a castable, a ramming mix and a plastic, respectively. It will be appreciated that many variations are possible within each of the broad types and that the teachings of the invention will apply to other monolith types such as mortars and gunning mixes of the wet or dry type.
The silicon carbide fines used in our invention are preferably about 325 mesh or finer and it is one of the distinctive and surprising features of our invention that such fine material, with high surface area and hence high protective value, can be employed without excessive oxidation loss in the absence of additions of glasses or fluxes to shield from oxidation. It is another surprising feature that the resulting structures are highly resistant to electric current and heat flow despite the silicon carbide inclusion.
Such fines are conveniently and inexpensively obtained as reject sizes in the preparation of cutting and polishing tools or as dust collector fines from plants preparing silicon carbide sizes for resale. incorporated within our mixes is the minimum amount which will exhibit the non-wetting melt-resistant eifects desired, the remainder is the aggregate.
The upper limit of silicon carbide fines usable is not controlled by loss of the melt resistant effects but rather by considerations such as cost, thermal conductivity, and overall size grading suitable to yield the necessary dense, tight structure essential for the operation of the invention. For example, 5 0% by weight of 325 mesh silicon carbon fines can not be incorporated into a castable mix without undesirably affecting density. Even coarser sizes of silicon carbide are effective in repelling slags and melts, although not nearly as effective as the finer sizes on a weight basis.
As a further example, while only 5%, by Weight, of
About 5% of such fines -325 mesh silicon carbide in a mix provides adequate +325 mesh. Thus when, for example, 20% of a 100.'
mesh type is added to a refractory mix the net result willbe incorporation of'about 6% of the most effiective 325 mesh particles. w
As an upper limit of -325 mesh silicon carbide, up to about 30% by weight may be included in the mix, which of course increases the degree of protection against. melt penetration, the 70% remainder is the aggregate. However, greater amounts, as the 50% by weight example above, are not usable since the desired dense, tight structure cannot be obtained.
Generally speaking, the refractory composition of this I invention is size graded so that the coarser, +65 mesh portion is the aggregate and the. fines are silicon carbide. Details of the silicon carbide sizing is set forth above. The aggregate is obtained by grinding or otherwise comminuting lump material until it substantially all just passes a 3 or 6 mesh screen. This material is referred to as -3 or 6 mesh material in the art to which this invention relates. The particle distribution curve which is descriptive of percentages on subsequent smaller sieves or screens is, of course, variable, depending on the lump material being considered. As a general rule, though, when to of selected aggregate of this invention has been reduced to pass a 3 or 6 mesh screen, from 50 to 90% is retained on a 65 mesh screen. Therefore, for purposes of this invention, the sizing of the alumina, aluminum ores, calcined fire clay, quartzite or gannister, and mixtures thereof (which serve as the aggregate of this invention) can therefore be described as follows: 80 to 90% being --3 to 6-mesh with 50 to 90% thereof resting on a 65 mesh screen. The remaining portions of the aggregate are coarser than 3 or 6 mesh and finer than 65 mesh. For further information of the propriety of so describing the sizing of refractory material see ASTM designation: E1 1-61 and page 1111 et seq. of The Chemical Engineers Handbook, Perry, third edition, published in 1950 by McGraw-Hill Book Company, Inc.
All laboratory evidence at this time indicates that finely divided silicon carbide additions to basic refractories are not as successful as they are with fireclay and high-alumina series. When basic refractories containing silicon carbide fiines are heated, they seem to invariably bloat and disrupt. In a fireclay or high-alumina base, when the very slow oxidation of silicon carbide seems to produce CO/CO and SiO a reaction occurs which produces mullite which is physically and chemically compatible, While in magnesia bases silica can cause'lowmelting phases.
Certain other refractory oxides are compatible with the bases and additions of this invention, as is illustrated by Mix F of Table III, which contains a quartzite component. 7
Having thus described the invention in detail and with sufi'icient particularity as 'to enable those skilledin the art to practice it, what is desired to have protected by Letters Patent is set forth in the following claims.
We claim:
1. A particulate, unformed refractory material, consisting essentially of, by weight, about 70 to of at least one ingredient material selected from the group consisting of alumina, aluminum ores, and fire clay, said ingredient material being 80 to 90% 3 mesh with 50 to 90% thereof being +65 mesh, and about 5 to 30% of silicon carbide, said silicon carbide being to --325 mesh, said refractory material being free of ingredients which will vitrify at temperatures of about 2100 F.
, 2. A refractory material according to claim 1 in which said silicon carbide is at least about 5% --325 mesh.
3. A refractory material according to claim 1 in which substantially all of the silicon carbide is reduced to about 100 mesh.
4. An unfired refractory shape consisting essentially of, by weight, about 70 to 95% of at least one ingredient ma terial selected from the group consisting of alumina, aluminum ores, and calcined fire clay, said ingredient material being 80 to 90% '3 mesh with 50 to 90% thereof being +65 mesh, and about 5 to 30% of silicon carbide, said silicon carbide being 100 to +325 mesh, but at least about 5% being 325 mesh, and said shape being free of ingredients which will vitrify at temperatures of about 2100 F. and resistant to wetting by molten copper and its alloys at this temperature.
5. A particulate, unformed refractory mixture consisting essentially of, by weight, about 85% of fire clay and about 15% of 325 mesh silicon carbide said fire clay being 80 to 90% 3 mesh with 50 to 90% thereof being +28 to +65 mesh, the mixture being free of ingredients which'will vitrify at temperatures of about 2100 F.
6. A high alumina ramming mix consisting essentially of, by weight, about 80% of at least one material selected from the group consisting of alumina and aluminum ores, said material being 80 to 90% 3 mesh with 50 to 90% thereof being +28 to +65 mesh, and about 10% of --325 mesh silicon carbide, said mix being free of ingredients which will vitrify at temperatures of about 2100 F.
7. An unformed, particulate refractory material free of ingredients which will vitrify at temperatures of about 2100 F., and which material, when installed in a furnace resists wetting by molten copper and its alloys, consisting essentially of about 30 to 95 of at least one material selected from the group consisting of alumina, aluminum ores, and fireclay, said ingredient material being 80 to 90% '-3 mesh with 50 to 90% thereof being +65 mesh, about 5 to 30% of 100 mesh silicon carbide, the remainder of the material being up to about 25% quartzite and up to about 15 by weight, ball clay.
8. The refractory material of claim 7 in which a major portion of the material slected from the group consisting of alumina, aluminum ores, and fire clay, is about 3 mesh, and the quartzite is about 6 mesh.
9. A particulate, unformed refractory material consisting essentially of, by weight, about 40 to 95% of at least one ingredient material selected from the group consisting of alumina, aluminum ores, and fire clay, said ingredient material being 80 to 90% -3 mesh with 50 to 90% thereof being +65 mesh, and about 5 to 30% of silicon carbide, said silicon carbide being 100 to 325 mesh, and up to about 15 of said fireclay being 325 mesh ball clay as a plasticizer, said material being free of ingredients which will vitrify at temperatures of about 21.00 F.
10. An unfired refractory shape consisting essentially of, by weight, about 70 to 95 of at least one ingredient material selected from the group consisting of alumina, aluminum ores, and calcined fire clay, said ingredient material being 80 to 90% '-3 mesh with 50 to 90% thereof being +65 mesh, and about 5 to 30% of silicon carbide, said silicon carbide being 100 to -325 mesh, but at least about 5% being 325 mesh, and up to about 15 of said fire clay including --325 mesh ball clay as a plasticizer, said shape being free of ingredients which will vitrify at about 2100 F.
11. A particulate, unformed refractory mixture consisting essentially of, by weight, about 85 of fire clay of which up to about 15%, by weight, based on the total weight of the mixture, is -325 mesh ball clay, and about 15 of 325 mesh silicon carbide said fire clay being 80 to 90% 3 mesh with 50 to 90% thereof being +28 to +65 mesh, the mixture being free of ingredients which will vitrify at a temperature of about 2100 F.
12. A high alumina ramming mix consisting essentially of, by Weight, about 80% of at least one material selected from the group consisting of alumina and aluminum ores, said material being 80 to 90% 3 mesh with 50 to 90% thereof being +28 to +65 mesh, and about 10% of 325 mesh silicon carbide, said mix being free of ingredients which will vitrify at a temperature of about 2100 F.
13. An unformed, particulate refractory free of material which will vitrify at temperatures of about 2100 F., and which, when formed, is resistant to wetting by molten copper and its alloys at 2100 F., consisting essentially of 30 to 95% of at least one material selected from the group consisting of alumina, aluminum ores, and fire clay, said material being to -6 mesh with 50- to 90% thereof being +65 mesh, about 5 to 30% of mesh silicon carbide, the remainder of the material being up to about 25% quartzite and up to about 15%, by Weight, ball clay.
References Cited by the Examiner UNITED STATES PATENTS 789,452 5/05 Queneau 10644 2,141,600 12/38 Fisher 10644 2,246,226 6/41 Walton 106--64 2,388,080 10/ 45 Riddle 10644 2,407,135 9/46 Clark 10664 FOREIGN PATENTS 847,965 9/ 60 Great Britain.
TOBIAS E. LEVOW, Primary Examiner.

Claims (1)

1. A PARTICULATE, UNFORMED REFRACTORY MATERIAL, CONSISTING ESSENTIALLY OF, BY WEIGHT ABOUT 70 TO 95% OF AT LEAST ONE INGREDIENT MATERIAL SELECTED FROM THE GROUP CONSISTING OF ALUMINA, ALUMINUM ORES, AND FIRE CLAY, SAID INGREDIENT MATERIAL BEING 80 TO 90% -3 MESH WITH 50 TO 90% THEREOF BEING +65 MESH, AND ABOUT 5 TO 30% OF SILICON CARBIDE, SAID SILICON CARBIDE BEING -100 TO -325 MESH, SAID REFRACTORY MATERIAL BEING FREE OF INGREDIENTS WHICH WILL VITRIFY AT TEMPERATURES OF ABOUT 2100*F.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3344080A (en) * 1964-09-16 1967-09-26 Atomic Energy Authority Uk Refractory oxides doped with silicon carbide and silicon nitride
US3364975A (en) * 1964-11-24 1968-01-23 Monsanto Co Process of casting a molten metal with dispersion of fibrous form of beta silicon carbide
US3538205A (en) * 1966-10-14 1970-11-03 Hughes Aircraft Co Method of providing improved lossy dielectric structure for dissipating electrical microwave energy
US3992214A (en) * 1974-08-14 1976-11-16 Dresser Industries, Inc. Refractory castable
US5382555A (en) * 1993-10-22 1995-01-17 General Acquisition Corporation High alumina brick with metallic carbide and its preparation

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Publication number Priority date Publication date Assignee Title
US789452A (en) * 1904-08-22 1905-05-09 New Jersey Zinc Co Method of making composite-wall metallurgical vessels.
US2141600A (en) * 1938-12-27 Refractory for induction furnaces
US2246226A (en) * 1941-06-17 Refractory
US2388080A (en) * 1940-06-29 1945-10-30 Champlon Spark Plug Company Alumina and silicon carbide refractory
US2407135A (en) * 1946-09-03 Furnace lining
GB847965A (en) * 1957-11-13 1960-09-14 Murex Welding Processes Ltd Improvements in welding fluxes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2141600A (en) * 1938-12-27 Refractory for induction furnaces
US2246226A (en) * 1941-06-17 Refractory
US2407135A (en) * 1946-09-03 Furnace lining
US789452A (en) * 1904-08-22 1905-05-09 New Jersey Zinc Co Method of making composite-wall metallurgical vessels.
US2388080A (en) * 1940-06-29 1945-10-30 Champlon Spark Plug Company Alumina and silicon carbide refractory
GB847965A (en) * 1957-11-13 1960-09-14 Murex Welding Processes Ltd Improvements in welding fluxes

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3344080A (en) * 1964-09-16 1967-09-26 Atomic Energy Authority Uk Refractory oxides doped with silicon carbide and silicon nitride
US3364975A (en) * 1964-11-24 1968-01-23 Monsanto Co Process of casting a molten metal with dispersion of fibrous form of beta silicon carbide
US3538205A (en) * 1966-10-14 1970-11-03 Hughes Aircraft Co Method of providing improved lossy dielectric structure for dissipating electrical microwave energy
US3992214A (en) * 1974-08-14 1976-11-16 Dresser Industries, Inc. Refractory castable
US5382555A (en) * 1993-10-22 1995-01-17 General Acquisition Corporation High alumina brick with metallic carbide and its preparation

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